Synthesis and Studies of Magnetic Layered Host-Guest Materials

9311597 Nocera这个提议的动机是合理设计磁性物质的挑战。本研究将利用层状材料中可用的结构控制来研究分子相互作用和磁耦合之间的相互作用。磷酸盐层状寄主的晶内环境将为有机无机插层物在层间和彼此间的明确关系中定位提供脚手架。采用氧化还原法和离子交换插层法合成了层状磷酸盐和磷酸盐的磁性插层物。插入特别设计的等结构有机和无机的准磁性或抗磁性客体将允许探测层内、层-客体、客体-客体和更高阶的磁性相互作用。在顺磁插层的情况下，开壳轨道的形状和相对于层的排列的作用可以与通道内的任务方向联系起来进行评估。最后，提出了顺磁任务磁主层组装的探索路径。由于该提案解决了磁耦合的结构问题，因此将出现具有磁性定制性能的材料的合理设计的新策略。此外，在这个层状磁性材料合成程序中组装的结构-磁性相关性将为新的磁性预测结构理论的发展提供动力。虽然提议的工作的主要重点是合成，但机械模型的发展将根据需要在与大学凝聚态物理小组的既定合作中进行。* * *

9311597 Nocera This proposal is motivated by the challenge of rationally designing magnetic substances. This research will exploit the structural control available in layered materials to study the interplay between molecular interactions and magnetic coupling. The intracrystalline environments of phosphate layered hosts will provide the scaffolding to position organic inorganic intercalants in well-defined relationships to the layers and to each other. Magnetic intercalates of layered phosphate and phosphonate hosts will be synthesized by redox and ion-exchange intercalation methods. Insertion of specially designed isostructural organic and inorganic sets of para- or diamagnetic guests will permit the probe of intralayer, layer-guest, guest-guest, and higher order magnetic interactions. In the case of paramagnetic intercalants, the roles of the open-shell orbitals' shape and alignment relative to the layers can be assessed in connection with quest orientation within the galleries. Finally, an exploratory path is outlined to assemble magnetic host layers about paramagnetic quests. As this proposal addresses structural issues of magnetic coupling, new strategies for the rational design of materials with magnetically tailored properties will emerge. Additionally, the structure- magnetism correlations assembled in this layered magnetic materials synthesis program will provide impetus for the development of new predictive structural theories of magnetism. Although the primary focus of the proposed work is synthetic, development of mechanistic models will be pursued as needed within an established collaboration with the condensed matter physics group at the University. ***